Cyclic olefin-based polymers produced by using cyclic olefins as monomers have alicyclic structures in their main skeletons. Hence, such a cyclic olefin-based polymer is more likely to be amorphous, exhibits an excellent transparency and heat resistance, has a small photo-elastic coefficient, and also has such properties as a low water absorbing property, acid resistance, alkaline resistance, and a high electrical insulation property. For this reason, use of the cyclic olefin-based polymers has been examined in applications such as display applications (retardation films, diffusion films, liquid-crystal substrates, films for touch panels, light guide plates, protection films for polarizing plates, and the like), optical lens applications, optical disk applications (CD, MD, CD-R, DVD, and the like), optical fiber applications, optical film/sheet applications, and sealing applications for optical semiconductors. Particularly, out of such cyclic olefin-based polymers, hydrogenated products of cyclic olefin-based polymers obtained by ring opening metathesis polymerization of norbornene derivatives are known to exhibit an excellent transparency and heat resistance, and to have a characteristic of a small photo-elastic constant. Hence, such a hydrogenated product, as well as polycarbonate, has been used as retardation films for liquid crystal displays (LCD) and the like. For this reason, development of cyclic olefin-based polymers obtained by using norbornene derivatives has been in progress in recent years.
Under such circumstances, various methods for producing norbornene derivatives which serve as raw materials of the cyclic olefin-based polymers have been studied. For example, International Application Japanese-Phase Publication No. 2000-506183 (Document 1) discloses a method for producing a norbornene derivative using the Diels-Alder reaction, in which a cyclic diene is reacted with an olefinic compound to yield a norbornene compound, wherein the cyclic diene is added gradually during the reaction. However, when the method for producing a norbornene derivative using the Diels-Alder reaction as described in Document 1 is used as a method for producing a norbornene derivative having a phenyl group at the 5-position, the obtained norbornene derivative is a mixture of an endo isomer in which the configuration of the phenyl group is an endo configuration and an exo isomer in which the configuration of the phenyl group is an exo configuration (endo:exo=6 to 8:4 to 2, such a ratio varies depending on reaction temperature). Accordingly, the exo isomer is not able to be produced selectively. In addition, such an endo isomer and an exo isomer have almost no difference in stability. Hence, even when isomerization by subjecting the obtained mixture to heat, or an acid or base catalyst is attempted, it is not possible to obtain only the exo isomer. Note that a conventional method for producing a norbornene derivative using the Diels-Alder reaction is shown in the following Reaction Formula (I):
pp. 1946 to 1949 (Document 2) discloses a method for obtaining a 5-phenyl 2-norbornene derivative. In this method, in the presence of a catalyst formed from palladium and a phosphorus compound represented by the following General Formula (6):
(in Formula (6), n represents 1 or 2),a norbornadiene-based compound and a compound represented by the formula: X—R (in the formula, X represents a halogen, and R represents a phenyl group) are reacted with each other to form the 5-phenyl-2-norbornene derivative. The method for producing a norbornene derivative as described in Non-Patent Document 1 is capable of selectively producing a norbornene derivative at a high yield where the configuration of the phenyl group (a substituent at the 5-position) is an exo configuration. However, according to the method for producing a norbornene derivative as described in Document 2, when a substituted phenyl group having a substituent such as a t-butyl group or the like is attempted to be introduced as a substituent at the 5-position, a norbornene derivative in which the configuration of the substituted phenyl group is an exo configuration is not able to be produced at a high yield.
Moreover, J. CHEM. SOC., CHEM. COMMUN. issued in 1989 pp. 1368 to 1370 (Document 3) discloses a method for producing a norbornene derivative. In this method, by using palladium acetate, tetra-n-butylammonium chloride and potassium formate as a catalyst system, a norbornadiene and a phenyl iodide are reacted with each other to obtain a norbornene derivative. However, by the method for producing a norbornene derivative as described in Document 3, the reaction does not proceed at all when a phenyl bromide is used as a reactant instead of the phenyl iodide.